Electrolytic deposition of metals



Nov. 24, 1936. J. BlLLlTER ELECTROLYTIC DEPOSITION OF META-LS OriginalFiled Dec. 11, 1933 2 Sheets-Sheet l fin enfor- [fan Bz'llz'ler AlfyQ J.BlLLlTER 2,061,554

ELECTROLYTIC DEPOSITION OF METALS Original Filed Dec. 11, 1933 2Sheets-Sheet 2 1311497160 r.- an Bz'ZZz'Zer 5y r q Patented Nov. 24,1936 UNITED STATES PATENT OFFICE ELECTROLYTIC DEPOSITION or METALS JeanBilliter, Vienna, Austria, assignor to Copperweld Steel Company,Glassport, Pa.

cember 14, 1929 4 Claims. (01. 204-11) My invention refers to thedeposition of metals by electrolytic action and more particularly to theproduction of tubular metal shapes, which may either be tubes or tubulardeposits on another tube or on a wire or rod forming a core.

It is another object of my invention to provide cathodes for use in theelectrolytic process which are better suited and more efficient than theoathodes hitherto used for the same purpose. With these and otherobjects in view I will now describe my invention and how the same can beperformed, having reference to the drawings affixed to thisspecification and forming part thereof, in which various forms ofapparatus embodying my invention are illustrated diagrammatically. byway of example.

In the drawings Fig. 1 is an elevation, partly in vertical section, ofapparatus for depositing metal on an endless row, wire or tube extendinghorizontally across a cell or series of cells.

Fig. 2 is an elevation, drawn to a larger scale, of one of the polishingmembers shown in Fig. 1.

Figs. 3 and 4 are a vertical axial section and an end elevation,respectively, of apparatus for pulling a tubular wire or tube across thecell, while keeping same rotating about its own axis.

Fig. 5 is an elevation, partly in axial section, of means for connectingthe ends of two tubular cathodes.

Fig. 6 is a diagram showing means for forming molten metal into a rod orwire and introducing same into the cell.

Fig. 7 is an elevation, partly in axial section, of a pair of superposedcells with an endless cathode extending vertically across the cells.

Fig. 8 is an axial section of a stuifing box adapted for use withapparatus as shown in Fig. 7.

Referring to the drawings and first to Fig. 1, I is a trough containinga body 2 of a suitable electrolyte, which is kept in constantcirculation. In the practical operation of my invention I may employ aplurality of such cells, which may be connected in series, but in thedrawings only a single cell is shown. 3 are anodes disposed on thebottom and sidewalls of the cell and 4 is the cathode which has the formof an endless wire extending lengthwise across the cell, beingintroduced through a stuffing box 5 in one and leaving the cell throughanother stuifing box 6 in the other endwall. This wire is originallywound on a reel I mounted for rotation about an axis 8 in a ring 9 orworm wheel, which is set rotating by a worm I0, mounted in horizontalbearings II of a casing I2, ball bearings I3 inserted between the casingI2 and the worm wheel securing frictionless rotation of the worm wheelin the casing. The worm I0 is set rotating by a driving shaft I4extending alongside of the cell 5 I and acting on the 'worm by means ofbevel gearing I5. Guide wheels I6 mounted on the front wall of thetrough I near the stuffing box 5 serve for guiding the core wire 4(cathode) centrically with regard to the worm wheel 9.

Similar guide wheels II are mounted on the other endwall of the troughI. The wire 4, on which a tubular layer of metal has been deposited inthe cell by electrolytic action, is kept taut during its passage throughthe cell and is wound upon another reel I8 mounted on an axis I9extending across and secured in bearings of an annular worm wheel 20,which is also mounted for rotation in a casing 2| in which is supporteda worm 22 driven in exact synchronism with worm II] by the driving shaftI4 and bevel gearing 23. On the reel I8 is mounted a bevel gear \:im 24gearing with a bevel gear ring 25 fixed o the casing 2|.

Obviously rotation of the shaft I4, which may be driven by an electricmotor or by suitable transmission from some other power engine, willcause synchronous rotation of the worms III and 22, of the worm wheels 9and 2D and of the reels I and I8, whereby the core wire or cathode 4 iskept rotating about its longitudinal axis, while passing through thecell I. The reel I8 at the farther end of the cell being coupled bybevel gearing with the stationary toothed ring 25 is at the same timepositively rotated about its axis I9 and therefore exerts a constantpull on the wire 4. While in Fig. 1 the reel I8 is shown as beingcoupled directly with the ring 25, it is obvious that in order toprovide for a slow travel of the cathode wire 4 across the cell,suitable intermediate gearing may be inserted between the reel I8 andthe ring 25.

Before entering the cell the cathode wire 4 is preferably rinsed andcleaned and also polished by suitable means, which are preferablyoperatively connected with the worm wheel 9, so as to rotate with it. Inthis manner torsional strain on the wire 4 is avoided.

In order to prevent a slack in the cathode wire 4 during its passageacross the cell I provide suitable supports which may at the same timeserve for polishing the deposit 26 on the wire. 21, 21 are the supports,one of which is shown more particularly in Fig. 2. 28 is a strap-shapedsupport suspended from a slide 29, which is guided between rails 30extending on top of and along- 55 side of the trough I. In the support28 are radially mounted three polishing tools 3|, two being fiXcd to thesupport 28, while the third one is adjustably mounted in a sleeve 32acted upon by a spring 33, which tends to force the sleeve 32 and thetool 3| mounted therein towards the core wire 4. The slides 29 of allthe supports 28 are connected by a rod 34 mounted in bearings 35 on theend walls of the trough i, this rod being set reciprocating by aneccentric wheel 36 mounted on a shaft 31 and connected with rod 34 by aconnecting rod 38.

In Figs. 3 and 4 are shown means for pulling across the cell, instead ofthe core wire 4, a tubular cathode which cannot be wound around a reel.Here the reel is replaced by a pair of grooved clamping rollers 39, 40,the journals of which are mounted in stays 4| extending across andforming Dart of a worm wheel 42 which is mounted for rotation in acasing 43 and operated by a worm 44 acted upon by the driving shaft [4.The grooved rollers 39, 40 are coupled by means of gear wheels 45, 46and one of them is driven by means of intermediate gearing 41, 48 from abevel gear 49 meshing with and rolling on a stationary toothed rim 50fixed to the casing 43.

If the casing 2| with its reel and worm gear shown on the right handside of Fig. 1 is replaced by a device of the kind shown in Figs. 3 and4, a tubular cathode 5|, for instance a, lead tube having a copper shell52 deposited thereon in the cell I may be pulled across the cell by thecoacting rollers 39, 40 which firmly grip the composite tube, at thesame time exerting a pull on it, being set rotating by cooperation ofthe bevel wheel 49 with the toothed rim 50. Thus, while the tubularcathode, if of soft metal, may be unwound from a reel such as the oneshown on the left hand side of Fig. 1, the bending of the copper-coatedtube which might cause a detaching or breaking of the copper layer, iseffectfully avoided. The worm wheel 42 carrying the rollers 39, 40,being rotated in exact synchronism with the worm wheel 9, from which thecathode is being unwound, the cathode will rotate about its longitudinalaxis during its passage through the cell.

During this passage the polishing tools which also serve as guiding andsupporting means exert a compressive action on the metal deposited onthe core wire or tube, thereby rendering it denser. Being reciprocatedby the eccentric wheel 36 they also polish the surface of the depositedmetal.

In order to produce endless bitmetallic tubes, when the core wire ortube has been unwound from the reel and is about to enter theelectrolytic cell, the end 53 of this tube may be connected with the end54 of a fresh tube wound on another reel by means of a short connectingpiece 55, as shown in Fig. 5.

Instead of depositing metal on a finished wire or tube wound on a reel,I may also produce such wire or tube right at the cell by arranging inclose vicinity to the cell an extruding press filled with the coremetal, the wire or tube formed by extrusion entering the cell throughthe stuffing box 5 (Fig. 1).

The press for extruding solid metal may be replaced by a heated presscontaining molten metal rod or wire 60 ready to enter the cell I throughthe stuifing box 6|.

Instead of conducting the endless cathode across the cell or cells inhorizontal direction, I may also operate with a vertically extendingcathode, as illustrated for instance in Fig. 7, where the oathode tube70 enters a cylindrical cell H from above, extending downwardly througha projecting part 12 of the bottom into another cell 13, concentricallyarranged with regard to the first one etc. The

cells are mounted on supports 14 for rotation about their vertical axis,being formed with toothed rims 15, which are acted upon by gear wheels15 mounted on a driving shaft 11. Here the cells rotate, while thecathode I0 is pulled downwardly by a .suitable device, such as thecoacting rollers 39, 40 shown in Figs. 3 and 4. A stuffing box, which isparticularly adapted for use in connection with rotary cells, isillustrated in Fig. 8, where is an endless cathode wire, rod or tubeextending through a sleeve 91 which projects from below into the cell92, being closed at its bottom end by a stufiing box 93. The sleeve ismounted with ball-bearings 94 on a support 95 and is packed in the cellbottom by means of a stuffing box 96. The cell and sleeve are thus enabled to rotate about the cathode. Both the cell and sleeve are linedwith insulating material wherever they are in contact with theelectrolyte.

In practising my invention I have found that the detaching of the metaldeposits from the cathodes, more especially in the case of tubularshapes, is connected with considerable difiiculties, and I havetherefore taken recourse to certain cathode materials which I have foundto be particularly suitable for the purpose. It has already beensuggested to employ cathodes consisting of chromium or chromium alloys,but the ordinary chromium alloys as well as the silicon alloys generallyin use were found to be unsuitable as after some time the metaldeposited thereon by electrolytic action will either firmly adhere tothe cathode or will be pierced by holes. I have now found that thesedrawbacks are not encountered if cathodes are employed consisting ofabsolutely homogeneous alloys of chromium and/or silicon, i. e. alloysin which these metals are distributed absolutely uniformly. I have foundthat alloys of the kind described in the German Patent SpecificationsNos. 341,793 and 369,191, for instance iron silicide, chromium silicideand other iron and chromium alloys containing from 13 to 25 per centsilicon are particularly suitable for this purpose. The same applies tothe well known steel alloys described in U. S. patents to Strauss, Nos.1,316,817, 1,339,- 378, 1,404,907, 1,404,908, 1,533,712, and 1,587,614,which contain from 18 to 30 per cent chromium and up to 20 per centnickel, which are known under the name of non-rusting steel alloys.However of these steel alloys only the very best specimens, as far ashomogeneity is concerned, should be employed.

Instead of the metallic cathodes used inthe production of tubes, I mayalso employ nonmetallic plastic masses coated with graphite or the liketo render the surface conductive.

When using easily fusible metal cathodes, I may remove thesesubsequently from the tube deposited thereon by heating and fusing thecathode.

Various changes may be made in the details disclosed in the foregoingspecification without departing from the invention or sacrificing theadvantages thereof.

I claim:- 1. Apparatus for the electrolytic production of metal depositscomprising a cell, a body oi elec- ,,trolyte in said cell, a reel infront of said cell, means for causing rotation of said reel in the planeof its axis of revolution, a wire wound on said reel, means to the rearof said cell comprising a pair of clamping rollers for pulling said wireacross said cell and means for causing said pulling means to rotate insynchronism with said reel.

2. Apparatus for the electrolytic production of metal depositscomprising a cell, a body of electrolyte in said cell, means for causinga rodor wire-shaped cathode to pass continuously in a substantiallystraight line through the electrolyte and to rotate in said electrolyteand reciprocatory means for polishing the metal deposit during suchrotation.

3. Apparatus for the electrolytic production of metal depositscomprising a plurality of superposed cells, an anode in each cell, meansfor moving a cathode rod or wire through the cell bottoms and means forcausing rotation of said cells about said rod or wire.

4. Apparatus for the electrolytic production of metal depositscomprising a plurality of superposed cells, an anode in each cell, meansfor moving a cathode rod or wire longitudinally through the cell bottomsand means for causing rotation of said cells about said rod or wire.

, JEAN BILLI'I'ER.

